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Halide-templated tert-butylethynide Ag14 complexes undergo reversible exchange with copper(I) to afford a series of mixed Ag14−nCun (n = 1–6) species. Up to six silver atoms in the cluster can be replaced with copper(I) to give a core structure featuring a Ag8Cu6 rhombic dodecahedron. These clusters are useful models for investigating the chemical reactivity and photoluminescence of heterometallic d10–d10 systems.
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